Metathesis polymerized olefin composites including sized reinforcement material

ABSTRACT

A reinforced polyolefin article is provided which includes a sized reinforcement material incorporated in the article. The article may be prepared by polymerizing a cyclic olefin monomer in the presence of the sizing agent and a metathesis polymerization catalyst which includes ruthenium or osmium.

RELATED APPLICATION

The present application is a continuation of U.S. application Ser. No.09/148,459, now U.S. Pat. No. 6,040,363, filed Sep. 4, 1998, entitledMETATHESIS POLYMERIZED OLEFIN COMPOSITES INCLUDING SIZED REINFORCEMENTMATERIAL by inventors Mark W. Warner, Steven D. Drake and Michael A.Giardello, the contents of which are incorporated herein by reference.

This application claims the benefit under 35 U.S.C. §119 of co-pendingU.S. Provisional patent application Ser. No. 60/057,999 filed Sep. 5,1997.

FIELD OF THE INVENTION

The present invention relates to articles made of reinforced metathesispolymerized olefins and cycloolefins, incorporating reinforcingmaterials, and methods for producing the same. More particularly, theinvention relates to reinforced metathesis polymerized olefins andcycloolefins that are polymerized in the presence of a reinforcingmaterial coated with a coupling or sizing agent.

BACKGROUND PRIOR ART

Numerous polymers of olefins, especially polymers of cycloolefins,produced through metathesis polymerization reactions using a metathiesiscatalyst are technologically and commercially important materials.Especially important are polymers of cycloolefins that are producedthrough Ring Opening Metathesis Polymerization (ROMP) reactions. Manysuch materials are tough and rigid, and have excellent chemicalresistance. However, for many high performance applications, even higherstiffness and strength are desirable. In such applications, it isdesirable to provide for reinforcement of the polyolefin structure.

Fiber reinforced polymer structures, generally, are known in the polymerart. Fiber reinforcement of polymers such as poly-dicyclopentadiene orother polymers of strained ring cycloolefins has been taught by Leach inU.S. Pat. No. 4,708,969. Improving the physical properties of a glasscomposite polydicyclopentadiene by heat treatment; is taught by Silverin U.S. Pat. No. 4,902,560. A reinforced norbornene polymer matrixincluding a glass mat reinforcement is taught by Sugawara et al. in U.S.Pat. No. 5,063,103.

However, it has been a problem to provide for a good interface or goodadhesion between the reinforcement materials and polyolefins producedthrough metathesis polymerization reactions. Due to the poor interfacebetween the reinforcement material anti the polyolefin, stiffness andstrength are lost. Additionally, if such composite materials are exposedto fluids during use, the fluids “wick” along the surface of thereinforcement material, due to the poor adhesion, and eventually wet theentire reinforcement material. The presence of a fluid further adverselyaffects the adherence of the polyolefin to the reinforcement material,and causes further loss of stiffness and strength. The wicking can causethe resulting composite material to be permeable to liquid, making itnot feasible for use with liquids.

Coupling agents, also referred to as sizing agents, are generally knownin the polymer art to improve adhesion between reinforcement materialsand polymer matrixes. However, it is known that coupling agents, andother impurities, adversely affect traditional metathesis catalysts, andare not usable with such catalysts. U.S. Pat. No. 4,902,560,specifically teaches that in dealing with a metathesis producedreinforced polymer matrix, the reinforcing agent should be“substantially completely free of surface coatings” and that “physicalproperties of structures prepared with glass containing surfacetreatments such as, e.g., coupling or sizing agents, deteriorate uponpost-cure . . . ” See U.S. Pat. No. 4,902,560, Column 3, Lines 51-58.

U.S. Sugawara, et al. U.S. Pat. No. 5,063,103, teaches a method ofcoating a sized glass reinforcement mat with a hydrocarbon. Anor-bor-nene polymer is then polymerized with a metathesis catalystsystem in the presence of the hydrocarbon coated glass mat to form areinforced polymer structure. However, the metathesis catalyst nevercomes into contact with the sizing agent. The hydrocarbon binder layercovers the sizing agent such that it does not adversely affect themetathesis catalyst. The additional step of coating the sized glass matprior to exposing it to the catalyst is expensive, time consuming, andburdensome.

It is desirable to provide a reinforced composite of a metathesispolymerized olefin polymer, especially a ROMP reaction polymerizedcycloolefin polymer, and a process for making the same, wherein thepolymer is polymerized with a metathesis catalyst in the presence of areinforcing material having a coupling agent thereon, and the couplingagent provides for an improved interface between the polymer and thereinforcing material without significantly adversely affecting thepolymerization reaction.

SUMMARY OF THE INVENTION

The present invention addresses these needs by using coupling agentswhich render a reinforcing material more compatible for a betterinterface with an olefin polymer that is polymerized through ametathesis polymerization reaction, but do not adversely poison orotherwise adversely affect the metalhesis catalyst or the polymerizationreaction.

More particularly, a ruthenium or osmium carbene complex catalyst isused as the catalyst for the metathesis polymerization of olefinmonomers, and the polymerization reaction takes place with thecatalyst/monomer mixture in direct contact with a reinforcement materialcoated with a suitable coupling agent, and the coupling agent hasminimal poisoning or other adverse affect on the catalyst.

Other features and advantages of the invention will become apparent tothose skilled in the art upon review of the following detaileddescription and claims.

Before embodiments of the invention are explained in detail, it is to beunderstood that the invention is not limited in its application to thedetails of the composition and concentration of components set forth inthe following description. The invention is capable of other embodimentsand of being practiced or being carried out in various ways. Also, it isunderstood that the phraseology and terminology used herein is for thepurpose of description and should not be regarded as limiting.

DETAILED DESCRIPTION OF AN EMBODIMENT

The invention involves polymerization of olefins through olefinmetathesis reactions, especially Ring Opening Metathesis Polymerization(ROMP) reactions, with a ruthenium or osmium carbene complex metathesiscatalyst in the presence of a reinforcing material coated, or sized,with a coupling agent to produce polyolefinic composite materialsincorporating the sized reinforcement material. The coupling agentprovides for better adhesion between the reinforcement material and thepolyolefin.

Suitable ruthenium and osmium carbene complex catalysts, the methods ofsynthesizing such catalysts, and suitable olefin monomers as well as themethods for performing and controlling the polymerization reaction, aredisclosed in the following patents and patent application, all of whichare incorporated herein by reference: U.S. Pat. Nos. 5,312,940 and5,342,909; WO 97/20865.

Catalysts:

Generally suitable catalysts are ruthenium and osilum carbene complexcatalysts disclosed in the above cited references.

The preferred ruthenium and osmium carbenie complex catalysts includethose which are stable in the presence of a variety of functional groupsincluding hycdroxyl, thiol, thioetlher, ketone, aldehyde, ester, ether,amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate,isocyanate, carbodiimide, carboalkoxy, peroxy, anhydride, carbamate, andhalogen. When the catalysts are stable in the presence of these groups,the starting monomers, impurities in the monomer, the coupling agents,any substituent groups on the catalyst, and other additives may includeone or more of the above listed groups without deactivating thecatalysts.

The catalyst preferably includes a ruthenium or osmium metal center thatis in a +2 oxidation state, has an electron count of 16, and ispentacoordinated. These ruthenium or osmium carbene complex catalystsmay be represented by the formula:

where:

M is O or Ru;

R and R¹ may be the same or different and may be hydrogen or asubstituent group which may be C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₁-C₂₀alkyl, aryl, C₁-C₂₀ carboxylate, C₁-C₂₀ alkoxy, C₂-C₂₀ alkenyloxy,C₂-C₂₀ alkynyloxy, aryloxy, C₂-C₂₀ alkoxycarbonyl, C₁-C₂₀ alkylthio,C₁-C₂₀ alkylsulfonyl and C₁-C₂₀ alkylsulfiniyl. Optionally, thesubstituent group may be substituted with one or more groups selectedfrom C₁-C₅ alkyl, lhalide, C₁-C₅ alkoxy, and phuenyl. The phienyl groupmay optionally be substiLuted witIh one or more groups selected fromhalide, C₁-C₅ alkyl, and C₁-C₅ alkoxy. Optionally, the substituent groupmay be substituted with one or more functional groups selected fromhydroxyl, thiol, thioethler, ketone, aldehyde, ester, ether, amine,imine, amide, nitro, carboxylic acid, disulfide carbonate, isocyanate,carbodiimide, carboal koxy, peroxy, anhydride, carbamate, and halogen.In a preferred embodiment, R and R¹ are the same or different and may behydrogen, substituted aryl, uinsubstituted aryl, substituted vinyl, andunsubstituted vinyl; where the substituted aryl and substituted vinylare each substituted withl one or more groups selected from hydroxyl,thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide,nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide,carboalkoxy, peroxy, anhydride, carbamate, and halogen, C₁-C₅ allcyl,C₁-C₅ alkoxy, unsubstituted phenyl, and phenyl substituted with halide,C₁-C₅ alkyl or C₁-C₅ alkoxy;

X and X¹ may be the same or different and may generally be hydrogen orany anionic liganid. An anionic ligand is any ligand whic)h when removedfrom a metal center in its closed shell electron configuration has anegative charge. In a preferred embodiment, X and X¹ are thre same ordifferent and may be halogen, hydrogen or a substitLLent group selectedfrom C₁-C₂₀ alkyl, aryl, C₁-C₂₀ alkoxide, aryloxide, C₁-C₂₀alkyldiketone, aryldiketonate, C₁-C₂₀ carboxylate, aryl or C₁-C₂₀allcylsulfonate, C₁-C₂o alkylthio, C₁-C₂₀ alkylsulfonyl, and C₁-C₂₀alkylsulfinyl. The substituent groups may optionally be substituted withC₁-C₅ alkyl, halogen, C₁-C₅ akloxy or phenyl. The phenyl may beoptionally substituted with halogen, C₁-C₅ alkyl, or C₁-C₅ alkoxy. In amore preferred embodiment, X and X¹ are the same or different and may beCl, Br, I, H or a substituent group selected from benzoate, C₁-C₅carboxylate, C₁-C₅ alkyl, phenoxy, C₁-C₅ alkoxy, C₁-C₅ alkylthio, aryl,and C₁-C₅ alkyl sulfonate. The substituent groups may be optionallysubstituted with C₁-C₅ alkyl or a phenyl group. The pheniyl group mayoptionally be substituted with halogen, C₁-C₅ alkyl or C₁-C₅ alkcoxy. Inan even more preferred embodiment, X and X¹ are the same or differentand are selected from Cl, CF₃CO₂, CH₃CO₂, CFH₂CO₂, (CH₃)₃CO,(CF₃)₂(CH₃)CO, (CF₃) (CH₃)₂CO, PhO, MeO, EtO, tosylate, mesylate, andtrifluoromethanesulfonate. In the most preferred embodiment, X and X¹are both Cl; and L and L¹ may be the same or different and may begenerally be any neutral electron donor. A neutral electron donor is anyligand which, when removed from a metal center in its closed shiellelectron configuration, has a neutral charge. In a preferred embodiment,L and L¹ may be the same or different and may be phosphines, sulfonatedphospliines, phosphites, phiosphinites, phosphonites, arsines, stibines,ethers, amines, amides, sulfoxides, carboxyls, nitrosyls, pyridines, andthioethers. In a more preferred embodiment, L and L¹ are the same ordifferent and are phosphines of the formula PR³R⁴R⁵ where R³ is asecondary alkyl or cycloaklyl and R⁴ and R⁵ are the same or differentand are aryl, C₁-C₁₀ primary alkyl, secondary alkyl, or cycloaklyl. Inthe most preferred embodiment, L and L¹ are the same or different andare —P(cyclohexyl)₃, —P(cyclopentyl)₃, or —P(isopropyl)₃. L and L¹ mayalso be —P(phenyl)₃.

A preferred group of catalysts are those where M is Ru; R¹ and R areindependently hydrogen or substituted or unsubstituted aryl orsubstituted or unsubstituted vinyl; X and X¹ are Cl; and L and L¹ aretriphenylphosphines or trialkylphosphines such astricyclopentylphosphine, tricyclohexylphosphine, andtriisopropylphosphine. The substituted aryl and substituted vinyl. mayeach be substituted with one or more groups including C₁-C₅ alkyl,halide, C₁-C₅ alkoxy, and a phenyl group which may be optionallysubstituted with one or more halide, C₁-C₅ alkyl, or C₁-C5 alkoxygroups. The substituted aryl and substituted vinyl may also besubstituted with one or more functional groups including hydroxyl,thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide,nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide,carboalkoxy, peroxy, anhydride, carbamate, and halogen.

Particularly preferred catalysts can be represented by the formulas:

where Cy is cyclopentyl or cyclohexyl, and Ph is phenyl.

The most preferred catalysts can be represented by the formula:

where Cy is cyclopenotyl or cyclohexyl, and Ph is phenyl.

The catalysts described above are useful in p olymerization of a widevariety of olefin monomers tlhroug metatlesis pcolymerizationo,particularly ROMP of cycloolefins.

Monomaers:

Suitable monomers include olefinis that can be polymerized by any of theruthenium or osmium metathesis polymerization cat a lysts that werediscussed arbove.

The olefin monomers may be unfunctionalized or functionalized to containone or more functional groups selected from the group consisting ofhydiroxyl, thaiol, thioether, ketone, aldehyde, ester, ether, amine,imine, amidie, nitro, carboxylic acid, disulfide, carbonate, isocyanate,carbodiimide, carboalkoxy, peroxy, anhydride, carbamate, and halogen.The olefin may be a strained cyclic olefin, or unstrained cyclic olefin,each of which may be functionclized or unfunctionalized.

Preferred monomers include functionalized or unfunctionalized cyclicolefins that are polymerized through ROMP reactions. This polymerizationprocess includes contacting a functionalized or unfunctionalized cyclicolefin with a ruthenium or osmium metathesis catalysts discussed above.The cyclic olefins may be strained or unstrained and may be monocyclic,bicyclic, or multicyclic olefins. If the cyclic olefin isfunctionalized, it may contain one or more functional groups includinghydroxyl, thiol, thioether, ketone, aldlehyde, ester, ether, amine,imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate,carbodiimide, carboalkoxy, peroxy, anhydride, carbamate, and halogen.

Suitable cyclic olefin monomers include monomers disclosed in U.S. Pat.No. 4,943,621 to Janda, et al., U.S. Pat. No. 4,324,717 to Layer, andU.S. Pat. No. 4,301,306 to Layer, all of which are herein incorporatedby reference.

Suitable cyclic olefin monomers include norbornene-type monomers whichare characterized by the presence of at least one norbornene group whichcan be substituted or unsubstituted. Suitable norbornene type monomersinclude substituted norbornenes and unsubstituted norbornene,dicyclopentadiene, di(methyl) dicyclopentadiene,dilhydrodicyclopentadiene, cyclopentadiene trimers, tetramers ofcyclopentadiene, tetracyclododecene, and substitutedtetracyclododecenes. Common norbornene-type monomers can be representedby the following formulas:

wherein R and R¹ may be tlie same or different and may be hydrogen or asubstitute group which may be a halogen, C₁-C₁₂ alkyl groups, C₂-C₁₂alkylene groups, C₆-C₁₂ cycloalkyl groups, C₆-C₁₂ cycloalkylene groups,and C₁-C₁₂ aryl groups or R and R¹ together form saturated orunsaturated cyclic groups of from 4 to 12 carbon atoms with the two ringcarbon atoms connected thereto, said ring carbon atoms forming part ofand contributing to the 4 to 12 carbon atoms in the cyclic group.

Less common norbornene type monomers of the following formulas are alsosuitable:

wherein R and R¹ have the same meaning as indicated above and n isgreater than 1. For example, cyclopentadiene tetramers (n=2),cyclopentadiene pentamers(n=3) and hexacyclopentadecene (n=2) aresuitable monomers for use in this invention.

Other specific examples of monomers suitable for use in this inventioninclude:

ethylidenenorborniene,

methyltetracyclododecene,

methylnorborinene,

ethylnorbornene,

dimethylnorbornene and similar derivatives,

norbornadiene,

cyclopentene,

cycloheptene,

cyclooctene,

7-oxanorbornene,

7-oxanorboriiene derivatives,

7-oxabicyclo[2.2.1]hept-5ene derivatives,

7-oxanorbornadiene,

cyclododecene,

2-norbornene, also named bicyclo[2.2.1]-2-heptene and substitutedbicyclic norbornenes,

5-methyl-2-norbornene,

5,6-dimethyl-2-norbornene,

5-ethyl-2-norbornene,

5-butyl-2-norbornene,

5-hexyl-2-norbornene,

5-dodecyl-2-norbornene,

5-isobutyl-2-norbornene,

5-octadecyl-2-norbornene,

5-isopropyl-2-norbornene,

5-phenyl-2-norbornene,

5-p-toluyl-2-norbornene,

5-a-naphthyl-2-norbornene,

5-cyclohexyl-2-norbornene,

5,5-dimethyl-2-norbornene,

dicyclopentadiene (or cyclopentadiene dimer),

dihydrodicyclopentadiene (or cyclopentene cyclopentadiene codimer),

methyl-cyclopentadiene dimer,

ethyl-cyclopentadiene dimer,

tetracyclododecene, also named1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethyanonaphthalene

9-methyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]-4-dodecene, also named1,2,3,4,4a,5,8,8a-octahydro-2-metlhyl-4,4:5,8-dimethanonaphthalene

9-ethyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]-4-dodecene,

9-propyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]-4-dodecene,

9-hexyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]-4-dodecene,

9-decyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]-4-dodecene,

9,10-dimethyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]-4-dodecene,

9-ethlyl, 10-methyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]-4-dodecene,

9-cyclohexyl-tetracyclo[6.2.1.1^(3,6).0^(2,7)]-4-dodecene,

9-chloro-tetracyclo[6.2.1.1^(3,6).0^(2,7)]-4-dodecene,

9-bromo-tetracyclo[6.2.1.1^(3,6).0^(2,7)]-4-dodecene,

cyclopentadiene-trimer,

methyl-cyclopentadiene-trimer,

and the like.

In a preferred embodiment, the cyclic olefin is cyclobutene, dimethyldicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclononene,cyclodecene, cyclooctadiene, cyclononadiene, cyclododecene, norbornene,norbornadiene, 7-oxanorbornene, 7-oxanorbornadiene, anddicyclopentadiene; each of which may be functionalized orunfunctionalized. In a more preferred embodiment, the cyclic olefin isdicyclopentadiene. Suitable dicyclopentadiene is comniierciallyavailable, for example, from Lyondell uncler the trademarks Lyondell 108and Lyondell 103. Preferably, the olefin monomer has a ptirity greaterthan about 95 percent by weight.

This invention contemplates preparation of homopolymers, as well asrandom and block copolymers and terpolymers of tlhe suitable monomersdiscussed above.

Reinforcemenit Materials:

Suitable reinforcing materials include those that add to the strength orstiffness of the polymer composite when incorporated with the polymer.Reinforcing material can be in the forim of filaments, fibers, rovings,mats, weaves, fabrics, knitted material, cloth or other knownstructures. Preferably, the reinforcing material is in filament or fiberform or fibers that are knitted into a fabric.

Representative suitable reinforcement materials inscLude barium sulfate;minerals, such as glass, carbon, graphite, ceramic, boron, and the like;metallic materials; organic polymers, such as aromatic polyamidesinctuding the aramici fibers, such as Kevlar®, and polybenzimide,polybenzoxazol, polybenzothiazol, polyesters, and the like; polyolefins;fluoropolymer, such as Halar®; cellullosic materials; and other materialknown to be useful as reinforcing material for polymer systems. Examplesof othier commercially available reinforcing materials include thefollowing products: Fiberfrax® from Unifrax Corporation, Interfil® fromAkzo Nobel, and wollastonite from Nyco. Fiber glass or fiber glassknitted into a fabric are preferred.

Coupling/Sizing Agents:

The reinforcing materials are “sized”, i.e., treated or coated withi acoupling agent, often also referred to as a sizing or bonding agent, torender them more compatible for adhering with thle olefin polymermatrix. As used herein, “coupling agent” means any material that can beapplied to a reinforcing material that provides for an improvedinterface or adlhesion between the reinforcement materials and thepolyolefin.

“Compatable coupling agents” as used herein include those couplingagents that are capable of being used in the presence of the metathesispolymerization reactions, preferably Ring opening MetathesisPolymerization (ROMP) reactions, which are catalyzed with a ruthenium orosmium catalyst, without adversely affecting the catalyst or thepolymerization reaction. Compatable coupling agents include conventionalcoupling agents which do not include functional groups that will poisonor adversely effect the metathesis polymerization reaction or catalyst.

Compatable coupling agents include a variety of conventional chromium;silane; titanate; zirconate, zirco-aluminate, and hydroxyl terminatedamphaphilic coupling agents. Preferably, those which do not contain thefollowing functionalities: vinyl ethers; active oxygen functionalitiessuch as hydroperoxides or activated epoxides; acetylenes; and otherLewis bases that may poison or adversely affect the ruthenium or osntiumcatalyst.

In a more preferable embodiment, the coupling agents also do not includethiols, primary amines, terminal epoxides, and certain conjugated dienefunctionalities. However, in certain of these embodiments, where thecoupling agent is applied to the reinforcing material in an acidicenvironment, coupling agents having thiols, primary amines, terminalepoxides, and certain conjugated diene functionalities may be used.

In an even more preferable embodiment, the coupling agent does notinclude any of the following functionalities: vinyl ethers; activeoxygen functionalities such as hiydroperoxides and activated epoxides;terminal epoxides; thiols; acetylenes; certain conjugated dienes; aminesand other Lewis bases that may poison or adversely affect the rutheniumor osmium catalysts.

Preferable chromium coupling agents include chromium complexes such asmethacrylatochromic chloride complex, and other similar such complexesthat may contain larger alkyl groups, for example, ethacrylatochromiccomplexes, propacrylatochromic complexes, butacrylatochromic complexes,etc. The most preferred coupling agents include the methacrylatochromicchloride complex. Such methacrylatochromic chloride complex couplingagents are commercially available from Du Pont under the trademarkVolan®, Volan A®, or Volan L®.

Preferable silane coupling agents include the following chemicals listedbelow, which are commercially available from Degussa under thecorresponding Degussa Designation Number listed below:

Degussa Chemical Name Desig. No. Propyltrimethoxysilana Si103Octyltrimethoxysilane Si108 Octadecyltrimathoxysilane Si118Vinyltris(2-methoxyethoxy)silane Si210 3-Butenyltriethoxysilane Si2212-(3-Cyclonexenyl)ethyltriethoxysilane Si2223-Methacryloxypropyltriethoxysilane Si223 3-ChloropropyltriethoxysilaneSi230 3,4-Dichlorobutyltriethoxysilane Si233N-(3-Triethoxysilylpropylcarbarnoyl) Si254Bis(3-trimethoxysilylpropyl)monosulphane Si165Bis(3-trimethoxysilylpropyl)tetrasulphane Si167Bis(3-triethoxysilylpropyl)tetrasulphane Si69 (3-Triethoxysilylpropyl)tri- Si270 methylammoniumchloride⁵)(3-Triethoxysilylpropyl- Si275 dimethyloctadecylammoniumchloride⁵)

Other preferable silane coupling agents include the following chemicalslisted below, which are commercially available from Dow Corning underthe corresponding Dow Corning Designation Numher listed below:

Dow Corning Desig. Chemical Name No.3-(2-Aminoethylamino)-propyltrimethoxysilane Z-60203-Chloropropyltrimethoxysilane Z-6076 Dimethyldichlorosilane Z-1219Diphenyldichlorosilane Z-1223 Hexamethyldisilazane, commercial Z-6079g-Methacryloxypropyltrimethoxysilane Z-6030 Methyltrichlorosilane Z-1211Methyltrimethoxysilane Z-6070 Phenyltrichlorosilane Z-1216Vinyltriacetoxysilane Z-6075 Water Repellent(Proprietary) 772

Other preferable silane coupling agents include the following chemicalslisted below, which are commmercially available from Union Carbide underthe corresponding Union Carbide Designation Number listed

Union Carbide Desig. Chemical Name No. Octyltriethoxysilane A-137Methyltriethoxysilane A-162 Methyltrimethoxysilane A-163 Proprietarynon-ionic silane dispersing agent  A-1230 Vinyltriethoxysilane A-151Vinyltrimethoxysilane A-171 Vinyl-tris(2-methoxyethoxysilane) A-172gamma-Methacryloxypropyltrimethoxysilane A-174beta-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane A-186gamma-Mercaptopropytrimethoxysilane A-189 Polyazamide silane (50% inmethanol)  A-1387 gamma-ureidopropyltrialkoxysilane  A-1160 (50% inmethanol) gamma-isocyanatopropyltriethoxycilane  A-1310

Suitable titanate coupling agents are commercially available from Dupontunder the trademark Tyzor. Suitable zirconate coupling agents arecommercially available from Kenrich under the Trademark Ken-react, andsuitable zirco-aluminate coupling agents are commercially available fromRhone-Poulenc.

Suitable liydroxyl terminated amphaphilic coupling agents include thefollowing which are commercially available from Chartwell:

Trademark Functionality B-525 carboxy B-525.1 carboxy B-535.1 C₁₂-C₁₈B-600 sulfido

The coupling agent is applied to the reinforcing material prior to thepolymerization reaction wherein the reinforcing material is incorporatedinto the polyolefin article. Suitable methods for applying the couplingagent include dipping, spraying, brushing, rolling or other methodsknown in the art for applying a coupling agent to a reinforcingmaterial. The coupling agent is applied to the reinforcing material toprovide at least a partial coating and in an amount such that thecoupling agent improves the interface or adhesion between thereinforcing materials and the polyolefin.

Methods for Making Reinforced Articles:

The reinforced polyolefin composite articles are made using methods suchthat the metathesis polymerization of the monomer occurs in the presenceof the sized reinforcing materials. Suitable methods of making thereinforced articles include a variety of polymer processing techniques,such as: casting, centrifugal casting, pultrusion, molding, rotationalmolding, open molding, reaction injection molding (RIM), resin transfermolding (RTM), pouring, vacuum impregnation, surface coating, filamentwinding and othiecr methods known to be useful for producing reinforcedpolymer articles. Preferably, the reinforced polymer structures aremanufactured through centrifugal casting or filament winding.

The polymerization reaction is carried out within or on the casts, casttubes, molds, mandrels or other structures used in the above namedmethods, in the presence of the sized reinforcing material to createreinforced ietathesis polymerized polymer articles.

Reaction and Processing Conditions:

The parameters for the metathesis polymerization reactions used in thecurrent invention, such as the atmosphere, the ratio of catalyst tomonomer, the reaction temperatures, the solvents that may be used, theadditives and other agents that may be present during the polymerizationreaction, and the methods for carrying out the metathesis polymerizationare disclosed in the incorporated references identified above.

Generally the polymerization of the olefin is carried out by adding thedesired ruthenium or osmium carbene metathesis catalyst to the monomerstarting material which has been heated to a starting resin temperature.Alternatively, the catalyst may be first added to the monomer startingmaterial and the mnixture then heated to the required temperature. Thestarting resin temperature is not critical; but, as is known, thistemperature does affect the rate of the polymerization reaction.Generally the reaction temperature will be in the range of about 0° C.to about 100° C., and preferably about 25° C. to about 45° C.

The ratio of catalyst to starting material is not critical and canwithin the range from about 1:5 to about 1:200,000 by mole. Ratios ofcatalyst to starting material of between about 1:2,000 and 1:15,000 byiiole are preferred. The invention may be practiced usingcatalyst/starting material ratios outside of the above ranges.

The monomer starting material may optionally be refluxed, run throughabsorption purification, and degassed before the catalyst is added;although, none of these proceduries is necessary to practice theinvention.

If a gel modification additive, cross-linking agent, or other additiveis used it is preferred that the additives be added before the catalyst;although, thi is not critical.

Although it is preferred that the reaction be conducted in the absenceof a solvent this is not critical. Possible solvents that may be usedinclude organic, protic, or aqueous solvents which are inert under thereaction conditions. Examples of suitable solvents may include aromatichydrocarbons, chlorinated hydrocarbons, ethers, alipabtic hydrocarbons,alcohols, watler, or mixtures thereof.

After polymerization is complete (i.e., after the article has “cured”)the polyolefin article may be post cured to initiate increasedcross-linking. As is known, additional cross-linlking may beaccomplished by post-curing at an elevated temperature. As is well knownin the art, other methods may be used to postcure the polyolefinmaterial.

Unlike previous catalyst systems, the catalyst/monomer starting materialmixture employed by the present invention may remain liquid for aconsiderable period of time depending on the temperature and the amountof gel modification additive present. This characteristic of threpresent catalyst system allows polyolefin articles to be made using avariety of polymer processing techniques discussed above.

The monomer starting material may also include a flame-retarding agentto reduce the flammability of the polyolefin. The flame-retarding agentmust be capable of being usedi iin the presence of the metathesispolymerization reactions catalyzed with a ruthenium or osinium catalyst,without adversely affecting the catalyst or the polymerization reaction.Suitable flame-retarcling agents include conventional flame-retardingagents which do not include functional groups that will poison oradversely effect the metathesis polymerization reaction or catalyst.Such flame retardants are commercially available from Clariant under thetrademarks EXOLIT IFR-11 and EXOLIT IFR-10.

The monomer starting material may optionally include additives such asfillers, binders, plasticizers, pigments, dyes, etc., as is known in theart. However, because of the functional group tolerance of thecatalysts, additives which cannot be used with other catalyst systems inthe preparation of metathesis polymerized articles can be used.

The following examples are intended to exemplify embodiments of theinvention and are not to be construed as limitations thereof.

EXAMPLE

A two inch diameter reinforced polydicyclopentadiene (PolyDCPD) pipe wasproduced using a centrifugal casting method. A fiberglass fabric wasused as the reinforcing material. The fiberglass fabric was sized with amethacrylatochromic chloride conmplex coupling agent purchased from DuPont under the trademark “Volan”. The following components were mixed tomake the DCPD resin/catalyst mixture:

Ingredient Parts Per Hundred Resin DCPD Monomer 100 Catalyst* 0.083Triphenyl phosphine 0.0938 EXOLIT IFR-11 or 10 11.11 Ciba-Geigy Tinuvin123 0.10 Albermarle Ethanox 702 4.0 TOTAL 115.387*bis-(tricyclohexylphosphine)-benzylidine ruthenium dichloride

The following process steps were then used to produce the pipe:

1. The Volan Sized Fiberglass Fabric was rolled around a tube (mandrel)smaller than the inside diameter of the desired finished pipe. Thenumber of layers and weight of the fabric may vary with the diameter andpressure rating of the finished pipe.

2. The fabric and tube were inserted into the mold tube, and the tubewas spun at a high enough revolutions per minute (RPM) to “unwind” thefabric from the mandrel.

3. After the mandrel was withdrawn, plugs were inserted into each end ofthe mold tube. One of the plugs included a port which could be sealedafter injecting the resin/catalyst mixture into the tube through theport.

4. A premeasured amount of the above resin/catalyst mixture formulationwas injected into the tube through the port in the end plug. The amountof resin depends upon the desired wall thickness and diameter of thefinished pipe.

5. The tube was spun at a speed which will result in approximately 75G's of force on the outside of the mold tube. A temperature of 85-950°F. was maintained by keeping the temperature of the room in which thepipe was produced at this temperature. This insured that the mold, glassand resin are all the same temperature.

6. The tube was allowed to spin until the mixture gelled, which was forapproximately 30 minutes (the resin exothermed and gelled during thistime).

7. The mold tube and pipe were removed from the spinning machine andplaced in a post cure oven for 30 minutes at 300° F.

8. The pipe was removed from the mold tube, the ends of the pipe weretrimnmed, and the mold tube was recycled.

Upon removal of the pipe, no significant odor of DCPD was noticed,indicating minimal amounts of residual monomer after curing.

End caps were then adhesively bonded onto each end of the sized pipe sothat a hydrostatic pressure test could be performed. The hydrostaticpressure test was performed in accordance with ASTM procedure D1599. Thesized pipe was pressurized up to about 1500 pounds per sqtiare inch(psi) before failing by actually tearing the fiberglass fabric. Therewas no weepage up to this point, indicating that the pipe wassubstantially impermeable, and there was no pathway for leakage alongant unreacted monomer.

In a second test, the sized pipes had a liquid red clyde applied to theend of the pipe. The pipe made with tilt Volan sized fabric did notexhibit any red dye penietration or “wicking”, even after several hours.

COMPARATIVE EXAMPLE

In a comparative example, a control sample of two inch diameterreinforced PolyDCPD pipe was produced in tale same manner described inExample 1, except that the fiberglass fabric was sized with an aminosilane coupling agent.

Upon removal of the pipe after curing, heavy odor of DCPD was noticed,indicating unreacted DCPD monomer.

End caps were then adhesively bonded onto each end of the pipe so that ahydrostatic pressure test could be performed in accordance with ASTMprocedure D1599. At the city water pressure of approximately 80 psi,general weepage through the wall of the pipe was noted. It was laterdetermined that the water was being forced into the woven roving throughthe ends of the pipe, and out the woven roving due to the incompatiblefinish on the woven roving deactivating the catalyst at the interfacebetween the polymer and the reinforcing material.

In the second test, the amino-silane sized pipe had a liquid red dyeapplied to the end of the pipe. The pipe made with standard amino-silavesized woven roving “wicked” the red dye at least ½ inch along thereinforcing glass fibers within a few minutes.

We claim:
 1. A reinforced polyolefin article comprising: a) areinforcing material selected from the group consisting of bariumsulfate, glass, carbon, graphite, ceramic, boron, metallic materials,organic polymers, polyolefins, and fluoropolymers, wherein thereinforcing material is at least partially coated with a compatiblecoupling agent selected from the group consisting of chromium, silane,titanate, zirconate, and zircoaluminate; and wherein the coupling agentis functionalized with at least one functional group, with the provisothat the compatible coupling agent is other than a functionalized silanehaving a primary amine functional group or a terminal epoxide functionalgroup; b) a polyolefin prepared by polymerizing a cyclic olefin monomerin the presence of a metathesis polymerization catalyst of the formula:

 wherein: M is ruthenium or osmium; X and X¹ are either the same ordifferent and are any anionic ligand; L and L¹ are either the same ordifferent and are any neutral electron donor; R and R¹ are either thesame or different and are each independently hydrogen or a substituentselected from the group consisting of C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl,C₂-C₂₀ alkynyl, aryl, C₁-C₂₀ carboxylate, C₁-C₂₀ alkoxy, C₂-C₂₀alkenyloxy, C₂-C₂₀ alkynyloxy, aryloxy, C₂-C₂₀ alkoxycarbonyl, C₁-C₂₀alkylthio, C₁-C₂₀ alkylsulfonyl and C₁-C₂₀ alkylsulfinyl, wherein eachof the substituents is substituted or unsubstituted; and wherein themonomer includes an additive selected from the group consisting offillers, binders, plasticizers., pigments and dyes; and wherein thecoupling agent is disposed between the reinforcing material and thepolyolefin.
 2. The reinforced polyolefin article of claim 1 wherein theolefin monomer comprises a norbornene-type monomer.
 3. The reinforcedpolyolefin article of claim 1 wherein the olefin monomer comprisesdicyclopentadiene.
 4. A reinforced polyolefin article comprising: a) areinforcing material at least partially coated with a compatiblecoupling agent, wherein the coupling agent is functionalized with atleast one functional group, with the proviso that the compatiblecoupling agent is other than a functionalized silane having a primaryamine functional group or a terminal epoxide functional group; b) apolyolefin prepared by polymerizing a olefin monomer in the presence ofa ruthenium or osmium metathesis polymerization catalyst, wherein themonomer includes an additive; and wherein the coupling agent is disposedbetween the reinforcing material and the polyolefin.
 5. The reinforcedpolyolefin article of claim 4 wherein the metathesis polymerizationcatalyst is of the formula:

wherein: M is ruthenium or osmium; X and X¹ are either the same ordifferent and are any anionic ligand; L and L¹ are either the same ordifferent and are any neutral electron donor; and R and R¹ are eitherthe same or different and are each independently hydrogen or asubstituent selected from the group consisting of C₁-C₂₀ alkyl, C₂-C₂₀alkenyl, C₂-C₂₀ alkynyl, aryl, C₁-C₂₀ carboxylate, C₁-C₂₀ alkoxy, C₂-C₂₀alkenyloxy, C₂-C₂₀ alkynyloxy, aryloxy, C₂-C₂₀ alkoxycarbonyl, C₁-C₂₀alkylthio, C₁-C₂₀ alkylsulfonyl and C₁-C₂₀ alkylsulfinyl, wherein eachof the substituents is substituted or unsubstituted.
 6. The polyolefinarticle of claim 5 wherein M is Ru, X and X¹ are Cl, L and L¹ areP(Cy)₃, R is hydrogen and R¹ is —CHCPh₂.
 7. The polyolefin article ofclaim 4 wherein the additive is selected from the group consisting offillers, binders, plasticizers, pigments and dyes.
 8. The polyolefinarticle of claim 4 wherein the olefin monomer comprises anorbomnene-type monomer.
 9. The polyolefin article of claim 4 whereinthe olefin monomer comprises dicyclopentadiene.
 10. The polyolefinarticle of claim 4 wherein the coupling agent is selected from the groupconsisting of chromium, silane, titanate, zirconate, zircoaluminate, andhydroxyl terminated amphaphilic coupling agent.
 11. A reinforcedpolyolefin article comprising: a) a reinforcing material sclected fromthe group consisting of barium sulfate, glass, carbon, graphite,ceramic, boron, metallic materials, organic polymers, polyolefins, andfluoropolymers, wherein the reinforcing material is at least partiallycoated with a compatible coupling agent selected from the groupconsisting of chromium, silane, titanate, zirconate, and zircoaluminate;and wherein the coupling agent is functionalized with at least onefunctional group, with the proviso that the compatible coupling agent isother than a functionalized silane having a primary amine functionalgroup or a tenminal epoxide functional group; and b) a polyolefinprepared by polymerizing a cyclic olefin monomer in the presence of aruthenium or osmium metathesis polymerization catalyst, wherein thecoupling agent is disposed between the reinforcing material and thepolyolefin.
 12. The polyolefin article of claim 11 wherein the olefinmonomer comprises dicyclopentadiene.
 13. The polyolefin article of claim11 wherein the coupling agent functional group is other than a thiol, aprimary amine, a terminal epoxide, or a conjugated diene functionality.14. The polyolefin article of claim 11 wherein the metathesispolymerization catalyst is of the formula

wherein: M is ruthenium; X and X¹ are Cl; L and L¹ are independentlyselected from the group consisting of triphenylphosphines,tricyclopentylphosphines, tricyclohexylphosphines, andtriisopropylphosphines; and R and R¹ are either the same or differentand are each independently hydrogen, substituted or unsubstituted aryl,or substituted or unsubstituted vinyl.
 15. The polyolefin article ofclaim 14 wherein the aryl or vinyl are substituted with a functionalgroup selected from the group consisting of hydroxyl, thiol, thioether,ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylicacid, disulfide, carbonate, isocyanate, carbodiumide, carboalkoxy,peroxy, anhydride, carbamate, and halogen.
 16. The polyolefin article ofclaim 14 wherein L and L¹ are tricyclopentylphosphines, R is hydrogenand R¹ is phenyl.
 17. A reinforced polyolefin article comprising: a) areinforcing material aleast partially coated with a compatible couplingagent, crein the coupling agent is functionalized with at least onefunctional group, with the proviso that the compatible coupling agent isother than a functionalized silane having a primary amine functionalgroup or a terminal epoxide functional group; and b) a polyolefinprepared by polymerizing an olefin monomer in the presence of ametathesis polymerization catalyst of the formula:

 wherein: M is ruthenium or osmium; X and X¹ are either the same ordifferent and are independently selected from the group consisting ofhalogen, hydrogen, or a substituent group selected from C₁-C₂₀ alkyl,aryl, C₁-C₂₀ alkoxide, aryloxicle, C₃-C₂₀ alkyldiketonate,aryldiketonate, C₁-C₂₀ carboxylate, aryl or C₁-C₂₀ alkylsulfonate,C₁-C₂₀ alkylthio, C₁-C₂₀ alkylsulfonyl, and C₁-C₂₀ alkylsulfinyl,wherein the substitutent group is substituted or unsubstituted; L and L¹are either the same or different and are independently selected from thegroup consisting of phosphines, sulfonated phosphines, phosphites,phosphinites, phosphonites, arsines, stibines, ethers, amines, amides,sulfoxides, carboxyls, nitrosyls, pyridines, and thioethers; R and R¹are either the same or different and are each independently hydrogen ora substitutent selected from the group consisting of C₁-C₂₀ alkyl,C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, aryl, C₁-C₂₀ carboxylate, C₁-C₂₀ alkoxy,C₂-C₂₀ alkenyloxy, C₂-C₂₀ alkynyloxy, aryloxy, C₂-C₂₀ alkoxycarbonyl,C₁-C₂₀ alkylthio, C₁-C₂₀ alkylsulfonyl and C₁-C₂₀ alkylsulfinyl, whereineach of the substituents is substituted or unsubstituted.
 18. Thereinforced polyolefin article of claim 12 further comprising anadditive.
 19. The reinforced polyolefin article of claim 18 wherein theadditive is selected from the group consisting of fillers, binders,plasticizers, pigments and dyes.
 20. The reinforced polyolefin articleof claim 17 wherein the olefin monomer comprises dicyclopentadiene.